Modified conjugated diene polymer, modified rubber composition comprising same, and method for producing modified conjugated diene polymer

ABSTRACT

Disclosed are a method of preparing a modified conjugated diene-based polymer, a modified conjugated diene-based polymer prepared thereby, and a rubber composition and a tire, including the modified conjugated diene-based polymer. The method of preparing the modified conjugated diene-based polymer includes (a) polymerizing a vinyl aromatic monomer and a conjugated diene monomer using an organo-alkali metal compound in the presence of a hydrocarbon solvent, thus forming an active polymer having an alkali metal end; and (b) coupling or linking the active polymer having the alkali metal end with a compound represented by Chemical Formula 1 or 2.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a national phase entry under 35 U.S.C. §371 ofInternational Application No. PCT/KR2015/007512, filed Jul. 20, 2015,which claims priority to Korean Patent Application No. 10-2014-0097466,filed Jul. 30, 2014, the disclosures of which are incorporated herein byreference.

TECHNICAL FIELD

The present invention relates to a modified conjugated diene-basedpolymer, a modified rubber composition comprising the same, and a methodof preparing the same and, more particularly, to a modified conjugateddiene-based polymer containing a rubber component and a reinforcingagent, a modified rubber composition comprising the modified conjugateddiene-based polymer, and a method of preparing the modified conjugateddiene-based polymer, in which the rubber component includes diene-basedrubber having high tensile strength, wear resistance, and wet skidresistance, as well as improved heat build-up when mixed with silica asthe reinforcing agent.

BACKGROUND ART

Recently, the demand for vehicles to exhibit increased stability,durability and fuel economy is ongoing. Accordingly, there is a need todevelop rubber having high wet skid resistance and mechanical strengthand low rolling resistance, as a material for vehicle tires, especiallytire treads, which are in contact with roads.

Conventional tire treads are manufactured by mixing conjugateddiene-based rubber with an inorganic filler to improve the aboveproperties, but suffer from high hysteresis loss or low dispersibility.

In this regard, for example, Korean Patent Application Publication No.2005-0091988 discloses a modified polymer having high resilience andthus superior fuel economy, but the effect thereof is insufficient.

DISCLOSURE Technical Problem

Accordingly, the present invention has been made keeping in mind theabove problems encountered in the related art, and an object of thepresent invention is to provide a method of preparing a modifiedconjugated diene-based copolymer, which may exhibit high modificationefficiency and superior processability compared to those preparedthrough conventional preparation processes.

Technical Solution

In order to accomplish the above object, the present invention providesa method of preparing a modified conjugated diene-based polymer,comprising: (a) polymerizing a conjugated diene monomer, or a vinylaromatic monomer and a conjugated diene monomer, using an organo-alkalimetal compound in the presence of a hydrocarbon solvent, thus forming anactive polymer having an alkali metal end; and (b) coupling or linkingthe active polymer having the alkali metal end with a compoundrepresented by Chemical Formula 1 or 2 below.

(R¹, R² and R³ are each a C1-C20 hydrocarbon, and A is an amine)

(R¹, R² and R³ are each a C1-C20 hydrocarbon, and A is an amine)

In addition, the present invention provides a modified conjugateddiene-based polymer, which is configured such that the end of a randomcopolymer comprising a conjugated diene monomer and a vinyl aromaticmonomer is modified with a compound represented by Chemical Formula 1 or2.

In addition, the present invention provides a modified conjugateddiene-based polymer, which is configured such that the end of an activepolymer comprising a conjugated diene monomer is modified with acompound represented by Chemical Formula 1 or 2.

In addition, the present invention provides a modified conjugateddiene-based polymer rubber composition, comprising the modifiedconjugated diene-based polymer.

In addition, the present invention provides a tire, comprising themodified conjugated diene-based polymer rubber composition.

Advantageous Effects

According to the present invention, the method of preparing a modifiedconjugated diene-based polymer enables the production of a modifiedconjugated diene-based polymer, which exhibits high modificationefficiency compared to those prepared through conventional preparationprocesses, and also, has high tensile strength, wear resistance, and wetskid resistance, as well as improved heat build-up when mixed withsilica as a reinforcing agent.

BEST MODE

Hereinafter, a detailed description will be given of a method ofpreparing a modified conjugated diene-based polymer, a modifiedconjugated diene-based polymer prepared thereby, and modified rubberincluding the modified conjugated diene-based polymer, according to thepresent invention.

According to the present invention, the method of preparing a modifiedconjugated diene-based polymer comprises: (a) polymerizing a conjugateddiene monomer, or a vinyl aromatic monomer and a conjugated dienemonomer, using an organo-alkali metal compound in the presence of ahydrocarbon solvent, thus forming an active polymer having an alkalimetal end; and (b) coupling or linking the active polymer having thealkali metal end with a compound represented by Chemical Formula 1 or 2below.

(R¹, R² and R³ are each a C1-C20 hydrocarbon, and A is an amine)

(R¹, R² and R³ are each a C1-C20 hydrocarbon, and A is an amine)

In the method of preparing the modified conjugated diene-based polymeraccording to the present invention, a homopolymer may be obtained bypolymerizing the conjugated diene monomer alone, or a random copolymermay be obtained by copolymerizing the vinyl aromatic monomer and theconjugated diene monomer.

The conjugated diene monomer may include at least one selected from thegroup consisting of 1,3-butadiene, 2,3-dimethyl-1,3-butadiene,piperylene, 3-butyl-1,3-octadiene, isoprene, and 2-phenyl-1,3-butadiene.The conjugated diene monomer may be used in an amount of 60 to 100 wt %,preferably 60 to 85 wt %, and more preferably 60 to 80 wt %, based on100 wt % in total of the conjugated diene monomer and the aromatic vinylmonomer. When the conjugated diene monomer is used in an amount of 100wt % based on 100 wt % in total of the conjugated diene monomer and thearomatic vinyl monomer, an active polymer resulting from polymerizingonly the conjugated diene monomer, without the aromatic vinyl monomer,is formed.

The vinyl aromatic monomer may include at least one selected from thegroup consisting of styrene, α-methylstyrene, 3-methylstyrene,4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene,4-cyclohexylstyrene, 4-(p-methylphenyl)styrene, and1-vinyl-5-hexylnaphthalene. Preferably useful is styrene orα-methylstyrene. The vinyl aromatic monomer may be used in an amount of0 to 40 wt %, preferably 15 to 40 wt %, and more preferably 20 to 40 wt%, based on 100 wt % in total of the conjugated diene monomer and thearomatic vinyl monomer. When the vinyl aromatic monomer is used in anamount of 0 wt % based on 100 wt % in total of the conjugated dienemonomer and the aromatic vinyl monomer, an active polymer resulting frompolymerizing only the conjugated diene monomer, without the aromaticvinyl monomer, is formed.

The hydrocarbon solvent may be a hydrocarbon, or may include at leastone selected from the group consisting of n-pentane, n-hexane,n-heptane, isooctane, cyclohexane, toluene, benzene, and xylene, but thepresent invention is not necessarily limited thereto.

As used herein, the active polymer having an alkali metal end refers toa polymer comprising a polymer anion and an alkali metal cation, whichare coupled with each other.

The active polymer having an alkali metal end may be a random copolymercomprising a conjugated diene monomer and a vinyl aromatic monomer.

In the method of preparing the modified conjugated diene-based polymeraccording to the present invention, the polymerizing in (a) may beperformed with the additional use of a polar additive.

The polar additive may be a base, or may include ether, amine ormixtures thereof. Specifically, it may be selected from the groupconsisting of tetrahydrofuran, ditetrahydrofurylpropane, diethylether,cycloamylether, dipropylether, ethylenedimethylether,ethylenedimethylether, diethyleneglycol, dimethylether,tert-butoxyethoxyethane bis(2-dimethylaminoethyl)ether,(dimethylaminoethyl)ethylether, trimethylamine, triethylamine,tripropylamine, and tetramethylethylenediamine Preferably useful isditetrahydropropylpropane, triethylamine, or tetramethylethylenediamine.

The polar additive may be used in an amount of 0.001 to 50 g, preferably0.001 to 10 g, and more preferably 0.005 to 1 g, based on 100 g in totalof the added monomer.

The polar additive may be used in an amount of 0.001 to 10 g, preferably0.005 to 1 g, and more preferably 0.005 to 0.1 g, based on 1 mmol intotal of the added organo-alkali metal compound.

When the conjugated diene monomer and the aromatic vinyl monomer arecopolymerized, a block copolymer may be easily prepared due to thedifference in the reaction rates therebetween. However, when the polaradditive is added, the low reaction rate of the vinyl aromatic compoundmay be increased to thus obtain the microstructure of the correspondingcopolymer, for example, a random copolymer.

In (a), the polymerization may be exemplified by anionic polymerization.

Particularly, the polymerization in (a) may be living anionicpolymerization, in which an active end is obtained through a growthreaction involving anions.

Also, the polymerization in (a) may be either high-temperaturepolymerization or room-temperature polymerization.

High-temperature polymerization is a polymerization process thatcomprises adding the organometallic compound and then applying heat toincrease the reaction temperature, and room-temperature polymerizationis a polymerization process that takes place in such a way that heat isnot applied after the organometallic compound is added.

The polymerization in (a) may take place at a temperature ranging from−20 to 200° C., preferably 0 to 150° C., and more preferably 10 to 120°C.

Also, b) may be performed at 0 to 90° C. for 1 min to 5 hr.

The method of preparing the modified conjugated diene-based polymeraccording to the present invention may be carried out in a batch manner,or alternatively in a continuous manner using a single reactor or atleast two reactors.

The organo-alkali metal compound may be used in an amount of 0.01 to 10mmol, preferably 0.05 to 5 mmol, and more preferably 0.1 to 2 mmol,based on 100 g in total of the monomer.

The molar ratio of the organo-alkali metal compound and the compoundrepresented by Chemical Formula 1 may range from 1:0.1 to 1:10, or 1:0.5to 1:2.

According to the present invention, the method of preparing the modifiedconjugated diene-based polymer may be carried out in a batch manner, oralternatively in a continuous manner using a single reactor or at leasttwo reactors.

In addition, the present invention addresses a modified conjugateddiene-based polymer prepared by the above method.

The modified conjugated diene-based polymer may be, for example, ahomopolymer composed exclusively of a conjugated diene monomer, or arandom copolymer comprising a conjugated diene monomer and an aromaticvinyl monomer. The end of the active polymer comprising the conjugateddiene monomer may be modified with the compound represented by ChemicalFormula 1 or 2, and the end of the random copolymer comprising theconjugated diene monomer and the vinyl aromatic monomer may be modifiedwith the compound represented by Chemical Formula 1 or 2.

The chain comprising the conjugated diene monomer and the aromatic vinylmonomer may include the vinyl aromatic monomer in an amount of 0 to 40wt %, preferably 15 to 40 wt %, and more preferably 20 to 40 wt %, basedon 100 wt % in total of the conjugated diene monomer and the aromaticvinyl monomer. When the vinyl aromatic monomer is used in an amount of 0wt % based on 100 wt % in total of the conjugated diene monomer and thearomatic vinyl monomer, an active polymer resulting from polymerizingonly the conjugated diene monomer, without the aromatic vinyl monomer,is formed.

The modified conjugated diene-based polymer may have a Mooney viscosityof 20 or more, preferably from 30 to 150, and more preferably from 40 to120.

The modified conjugated diene-based polymer may have a number averagemolecular weight of 1,000 to 2,000,000 g/mol, preferably 10,000 to1,000,000 g/mol, and more preferably 100,000 to 500,000 g/mol.

The modified conjugated diene-based polymer may have a vinyl content of18 wt % or more, preferably 25 wt % or more, and more preferably 30 to70 wt %. Given the above vinyl content range, the glass transitiontemperature of the polymer may be elevated. Thus, when such a polymer isapplied to tires, the properties required of tires, such as runningresistance and wet grip, may be satisfied, and superior fuel economy mayresult.

The vinyl content refers to the amount of a monomer having a vinylgroup, or the amount of 1,2-added conjugated diene monomer rather thanthe amount of 1,4-added conjugated diene monomer, based on 100 wt % ofthe conjugated diene monomer.

The modified conjugated diene-based polymer may have a polydispersityindex (PDI) of 0.5 to 10, preferably 0.5 to 5, and more preferably 1.0to 2.0.

The modified conjugated diene-based polymer may exhibit viscoelasticproperties. When measured at 10 Hz using DMA after mixing with silica,Tan δ at 0° C. may be in the range of 0.6 to 1 or 0.9 to 1. Given theabove Tan δ range, desired skid resistance or wet resistance may beobtained.

Also, Tan δ at 60° C. may be in the range of 0.06 to 0.09 or 0.07 to0.08. Given the above Tan δ range, desired rolling resistance orrotational resistance (RR) may be obtained.

In addition, the present invention addresses a modified conjugateddiene-based polymer rubber composition comprising 0.1 to 200 parts byweight of an inorganic filler based on 100 parts by weight of themodified conjugated diene-based polymer.

The amount of the inorganic filler may be 10 to 150 parts by weight or50 to 100 parts by weight.

The inorganic filler may include carbon black, silica, or a mixturethereof.

The inorganic filler may be silica. As such, dispersibility issignificantly increased, and the end of the modified conjugateddiene-based polymer of the invention may be coupled (capped) with silicaparticles, thus significantly decreasing hysteresis loss.

The modified conjugated diene-based polymer rubber composition mayfurther comprise an additional conjugated diene-based polymer.

Examples of the additional conjugated diene-based polymer may includeSBR (styrene-butadiene rubber), BR (butadiene rubber), natural rubber,and mixtures thereof.

SBR may be exemplified by SSBR (solution styrene-butadiene rubber).

The modified conjugated diene-based polymer rubber composition accordingto the present invention may comprise 20 to 100 parts by weight of themodified conjugated diene-based polymer and 0 to 80 parts by weight ofthe additional conjugated diene-based polymer.

Alternatively, the modified conjugated diene-based polymer rubbercomposition according to the present invention may comprise 20 to 99parts by weight of the modified conjugated diene-based polymer and 1 to80 parts by weight of the additional conjugated diene-based polymer.

Alternatively, the modified conjugated diene-based polymer rubbercomposition according to the present invention may comprise 10 to 100parts by weight of the modified conjugated diene-based polymer, 0 to 90parts by weight of the additional conjugated diene-based polymer, 0 to100 parts by weight of carbon black, 5 to 200 parts by weight of silica,and 2 to 20 parts by weight of a silane coupling agent.

Alternatively, the modified conjugated diene-based polymer rubbercomposition according to the present invention may comprise 10 to 100parts by weight of the modified conjugated diene-based polymer, 0 to 90parts by weight of the additional conjugated diene-based polymer, 0 to100 parts by weight of carbon black, 5 to 200 parts by weight of silica,and 2 to 20 parts by weight of a silane coupling agent, in which thetotal weight of the modified conjugated diene-based polymer and theadditional conjugated diene-based polymer may be 100 parts by weight.

Alternatively, the modified conjugated diene-based polymer rubbercomposition according to the present invention may comprise 100 parts byweight of a polymer mixture comprising 10 to 99 wt % of the modifiedconjugated diene-based polymer and 1 to 90 wt % of the additionalconjugated diene-based polymer, 1 to 100 parts by weight of carbonblack, 5 to 200 parts by weight of silica, and 2 to 20 parts by weightof a silane coupling agent.

Also, the modified conjugated diene-based polymer rubber compositionaccording to the present invention may further comprise 1 to 100 partsby weight of oil.

The oil may be exemplified by mineral oil or a softener.

The oil may be used in an amount of 10 to 100 parts by weight or 20 to80 parts by weight based on 100 parts by weight of the conjugateddiene-based copolymer. Given the above oil content range, desiredproperties may be exhibited, and the rubber composition may beappropriately softened, thus increasing processability.

The modified conjugated diene-based polymer rubber composition may beused to manufacture, for example, a tire or a tire tread.

According to the present invention, a tire is manufactured using themodified conjugated diene-based polymer rubber composition.

A better understanding of the present invention may be obtained via thefollowing examples, which are merely set forth to illustrate the presentinvention, and those skilled in the art will appreciate that variouschanges and modifications are possible, without departing from the scopeand spirit of the invention as disclosed in the accompanying claims.

MODE FOR INVENTION EXAMPLE Preparation of modified conjugateddiene-based polymer Example 1

A 10 L reactor with a stirrer and a jacket was preliminarily dried withnitrogen, after which 777 g of butadiene, 273 g of styrene, 4800 g ofhexane, and 0.85 g of TMEDA as a polar material were placed in thereactor without impurities, and the temperature inside the reactor wasmaintained at 50° C.

As a polymerization initiator, n-butyllithium (Chemetal) was fed in anamount of 0.5 g, based on solid content, into the reactor. After theinitiation of the reaction, the temperature inside the reactor began torise due to the heat generated due to the polymerization, and thus thefinal temperature inside the reactor reached 80° C. After thetermination of the polymerization, 5.25 mmol of Modifier A(3-(2-ethoxy-5,5-dimethyl-1,3,2-dioxasilinan-2-yl)-N,N-dimethylpropan-1-amine)was placed in the reactor, and a modification reaction was carried outfor 5 min at a temperature of 80° C. The resulting polymer solution wasadded with 2.1 g of 2,6-di-t-butyl-p-cresol (BHT) as an antioxidant,followed by steam stripping to remove the solvent and then drying in anoven, yielding a sample (styrene-butadiene copolymer) having a modifiedcomponent.

Example 2

A sample (styrene-butadiene copolymer) having a modified component wasobtained in the same manner as in Example 1, with the exception thatModifier B(3-(2-ethyl-5,5-dimethyl-1,3,2-dioxasilinan-2-yl)-N,N-dimethylpropan-1-amine)was used in lieu of Modifier A in the same equivalent amount.

Comparative Example 1

A sample (styrene-butadiene copolymer) having a modified component wasobtained in the same manner as in Example 1, with the exception that aSiCl₄ modifier was used in lieu of Modifier A in the same equivalentamount.

Comparative Example 2

A sample (styrene-butadiene copolymer) having a modified component wasobtained in the same manner as in Example 1, with the exception thatModifier C(3-(diethoxy(methyl)silyl)-N-(3-(diethoxy(methyl)silyl)propyl)-N-methylpropan-1-amine)was used in lieu of Modifier A in the same equivalent amount.

Test Example

The modified conjugated diene-based polymers of the examples andcomparative examples were measured for Mooney viscosity, modificationefficiency, molecular weight distribution via GPC, RR, wet grip, andwear resistance. The results are shown in Table 1 below.

1. Measurement of Mooney Viscosity

The viscosity of rubber was measured using a Mooney viscometer (ALPH ATechnologies, Mooney MV 2000). For this, a rubber sample weighing 25 to30 g was measured at 100° C. using a large rotor with a preheating timeof 1 min and a testing time of 4 min [ML₁₊₄(100° C.)].

2. Measurement of Modification Efficiency

The modification efficiency was measured using a bound rubbermeasurement method. Specifically, about 0.2 g of the mixture, resultingfrom secondary kneading, was cut into the shape of a cube, each side ofwhich was about 1 mm, placed in a 100-mesh stainless steel screen box tomeasure the weight thereof, immersed in toluene for 24 hr, and dried,after which the weight thereof was measured.

The amount of filler-bound rubber was calculated from the amount of thecomponent that was not dissolved but remained, thus determining theratio of the amount of filler-bound rubber relative to the amount ofrubber in the first mixture. The value thus determined was used as themodification efficiency.

A more detailed description thereof is as follows.

1) A cubic box having a volume of 1 cm³ (1 cm×1 cm×1 cm) was made of a100-mesh stainless steel screen. The weight thereof was accuratelymeasured to the third decimal place (Wo).

2) About 1 g of a cured rubber sample was uniformly cut to a size of 1mm×1 mm×1 mm, and then the weight thereof was accurately measured to thethird decimal place (W1).

3) The rubber sample was carefully placed in the cubic mesh box and thencovered with a lid so as to prevent the loss of the sample.

4) 1000 cc of toluene was placed in a 2 L glass bottle (having arectangular parallelepiped shape), and the mesh box containing thesample was immersed in the toluene bottle. The sample box was located ata central position in the solution.

5) The sample immersed in the solution was allowed to stand for 14 days.Here, care was taken to avoid stirring the solution, attributable to thetransfer or shaking of the bottle.

6) After 14 days, the mesh box containing the sample was taken out ofthe solution and then dried in a vacuum oven at 140° C. for 35 min.

7) The weight of the dried sample (mesh box+sample) was measured (W2).

8) (W2-Wo) was calculated, thus determining the amount of the sampleremaining after extraction (W3).

9) The amount of rubber and the amount of inorganic material containedin W1 were calculated (the amounts of rubber and inorganic fillercontained in 1 g of compound were calculated using the mixing recipe).(Theoretical amount of rubber=W4, Theoretical amount of inorganicmaterial=W5)

10) The amount of B-rubber was calculated.B-rubber %=[(W3−W5)/(W4)]*100

3. Rolling Resistance (RR) and Wet Grip

The RR and wet grip of rubber were measured using DMTS (Dynamicmechanical thermal spectrometry; GABO, EPLEXOR 500N). The measurementconditions were as follows: frequency: 10 Hz, strain (static strain: 3%,dynamic strain: 0.25%), and temperature: −60 to 70° C. As such, RR wasdetermined based on Tan δ at 60° C., and wet grip was determined basedon Tan δ at 0° C. These values were represented as indexes relative tothe value of Comparative Example 1, which was set to 100.

4. Wear Resistance

The wear resistance of rubber was determined using the DIN abrasionperformance index calculation method based on ASTM D 5963-97a.

(Relative Volume Loss)Wear loss (mg) of test sample×200 (mg)/specific gravity of testsample×wear loss (mg) of reference sample

TABLE 1 Ex. 1 Ex. 2 C. Ex. 1 C. Ex. 2 Modifier Modifier A Modifier BSiCl₄ Modifier C Mooney viscosity 89 85 90 88 Modification 92 87 10 90efficiency RR index 113 115 100 110 Wet index 117 108 100 112 Wearresistance 110 110 100 108

As is apparent from Table 1, the modification efficiency of the samplesof Examples 1 and 2 according to the present invention was much higherthan that of Comparative Example 1, and was similar to that ofComparative Example 2. Also, the samples of Examples 1 and 2 manifestedsuperior wear resistance, RR and wet grip.

The invention claimed is:
 1. A method of preparing a modified conjugateddiene-based polymer, comprising: (a) polymerizing a conjugated dienemonomer, or a vinyl aromatic monomer and a conjugated diene monomer,using an organo-alkali metal compound in presence of a hydrocarbonsolvent, thus forming an active polymer having an alkali metal end; and(b) coupling or linking the active polymer having the alkali metal endwith a compound represented by Chemical Formula 1 or 2 below

(R¹, R² and R³ are each a C1-C20 hydrocarbon, and A is an amine)

(R¹, R² and R³ are each a C1-C20 hydrocarbon, and A is an amine).
 2. Themethod of claim 1, wherein the active polymer is a random copolymercomprising the conjugated diene monomer and the vinyl aromatic monomer.3. The method of claim 2, wherein the random copolymer contains theconjugated diene monomer and the vinyl aromatic monomer in a ratioranging from 90:10 to 60:40.
 4. The method of claim 1, wherein theactive polymer contains the conjugated diene monomer and the vinylaromatic monomer in a ratio ranging from 100:0 to 60:40.
 5. The methodof claim 1, wherein the organo-alkali metal compound is used in anamount of 0.01 to 10 mmol based on 100 g in total of the monomer(s). 6.The method of claim 1, wherein a molar ratio of the organo-alkali metalcompound and the compound represented by Chemical Formula 1 is 1:0.1 to1:10.
 7. The method of claim 1, wherein the polymerizing in (a) isperformed with additional use of a polar additive.
 8. The method ofclaim 7, wherein the polar additive is added in an amount of 0.001 to 50g based on 1 mmol in total of the organo-alkali metal compound.
 9. Amodified conjugated diene-based polymer, which is configured such thatan end of a random copolymer comprising a conjugated diene monomer and avinyl aromatic monomer is modified with a compound represented byChemical Formula 1 or 2 below

(R¹, R² and R³ are each a C1-C20 hydrocarbon, and A is an amine)

(R¹, R² and R³ are each a C1-C20 hydrocarbon, and A is an amine). 10.The modified conjugated diene-based polymer of claim 9, wherein therandom copolymer contains the conjugated diene monomer and the vinylaromatic monomer in a ratio ranging from 90:10 to 60:40.
 11. A modifiedconjugated diene-based polymer rubber composition, comprising themodified conjugated diene-based polymer of claim
 9. 12. The modifiedconjugated diene-based polymer rubber composition of claim 11, whereinthe modified rubber composition comprises 20 to 90 wt % of the modifiedconjugated diene-based polymer based on a total weight of thecomposition.
 13. The modified conjugated diene-based polymer rubbercomposition of claim 11, wherein the modified rubber compositioncomprises 0.1 to 200 parts by weight of an inorganic filler based on 100parts by weight of the modified conjugated diene-based polymer.
 14. Themodified conjugated diene-based polymer rubber composition of claim 13,wherein the inorganic filler is silica.
 15. The modified conjugateddiene-based polymer rubber composition of claim 11, wherein the modifiedrubber composition comprises 0.1 to 200 parts by weight of an inorganicfiller based on 100 parts by weight of the modified conjugateddiene-based polymer.
 16. A tire, comprising the modified conjugateddiene-based polymer of claim
 9. 17. A modified conjugated diene-basedpolymer, which is configured such that an end of an active polymercomprising a conjugated diene monomer is modified with a compoundrepresented by Chemical Formula 1 or 2 below

(R¹, R² and R³ are each a C1-C20 hydrocarbon, and A is an amine)

(R¹, R² and R³ are each a C1-C20 hydrocarbon, and A is an amine).
 18. Amodified conjugated diene-based polymer rubber composition, comprisingthe modified conjugated diene-based polymer of claim
 17. 19. Themodified conjugated diene-based polymer rubber composition of claim 18,wherein the modified rubber composition comprises 20 to 90 wt % of themodified conjugated diene-based polymer based on a total weight of thecomposition.
 20. A tire, comprising the modified conjugated diene-basedpolymer of claim 17.